Polyolefin blends with occluded nitrogenous heterocyclic polyamides in the fibers differentially dispersed dyed

ABSTRACT

A method and article resulting from differentially dyeing a composite material by producing at least two fibers of the same spinnable polymeric composition possessing different concentrations of the same dye-reception promoter, forming said fibers into a composite material such as fabric or carpet and piece dyeing said composite material to produce different shades of the same color by contact with a suitable dye.

United States Patent [191 Johnson 1 POLYOLEFIN BLENDS WITH OCCLUDED NITROGENOUS HETEROCYCLIC POLYAMIDES IN THE FIBERS DIFFERENTIALLY DISPERSEI) DYED [75] Inventor: Robert F. Johnson, Lubbock, Tex.

[73] Assignee: Phillips Petroleum Company,

Bartlesville, Okla.

22 Filed: Dec. 6, 1971 [21] Appl. No.: 205,401

Related US. Application Data [63] Continuation-impart of Ser. No. 812,892, April 2,

1969, abandoned.

[52] U.S. Cl. 8/21 B, 8/168, 8/2] C, 8/21 D, 8/31 [51] Int. Cl D06p 3/86 [58] Field of Search 8/21 C, 21 B, 21 A, 15; 57/140 BY [56] References Cited UNITED STATES PATENTS 2,475,672 6/1949 Mellor et a1. 8/15 in] 3,820,949 June 28, 1974 2,922,690 1/1960 Mueller et a1. 8/174 3,389,549 6/1968 David 57/140 R 3,652,198 3/1972 7 Farber et a1. 8/21 C OTHER PUBLICATIONS Dupont, Textile Fibers Technical Information Multifibers, Bulletin X-lOO, Feb. 1959, 4 pages.

Primary Examiner-Donald Levy 57 ABSTRACT 15 Claims, No Drawings 1 POLYOLEFIN BLENDS WITH OCCLUDED NITROGENOUS HETEROCYCLIC POLYAMIDES IN THE FIBERS DIFFERENTIALLY DISPERSED DYED This application is a continuation-in-part of US. Pat. application Ser. No. 812,892, filed Apr. 2, 1969 now abandoned.

This invention relates to differentially dyeing a composite material. More particularly, it relates to the dyeing of synthetic fibers with disperse dyes to obtain multishade effects. 1

The production and utilization of spinnable polymeric compositions has assumed great industrial importance in recent years. Of the various polymeric compositions that are adaptable to spinning into fiber, polypropylene is one of the most significant. Although polypropylene can be satisfactorily spun into a fiber, the polypropylene must then in turn be colored in order to produce certain varieties of commercially marketable products known as composite materials. A composite material is defined by this application to consist of the result of combining at least two fibers into a product. Examples include fabric, carpet, yarn and the like.

Composite materials can be uniformly colored, or can have several different colors or can be difierentially colored so as to contain at least two different shades of the same color. The differential color resulting from different shades of the same color existing in the composite material can result from dyeing, in which case a differentially dyed composite material results.

Dyeing of composite materials to produce color can be accomplished in a variety of ways. The individual fibers can be dyed or the composite material produced and then the composite material piece dyed. Thus, ac cording to this technique, piece dyeing occurs when the composite material is contacted as a unit with the dye ing medium. Examples of piece dyeing include dyeing a fabric by passing the fabric through a fog or a mist of dye or immersing a carpet in a bath of dye.

The differential dyeing of composite materials to obtain tone-on-tone, i.e., multi-shade, effects demands considerable knowledge on the part of the dyer with respect to the various classes of dyes, the dyeing properties of the fibers and, of greater difficulty, the various behaviors of particular individual dyes. Some fibers can be successfully tone-on-tone dyed with some dyestuffs but not with others. In many instances, there is such a tendency to streakiness of dye takeup that it is necessary to use broken-up patterns such as tweed or moresque or to employ combinations of fibers such as a dye-receptive fiber, a pigmented fiber and a nondyeable fiber. In still other instances, it is necessary to employ mixtures of dyestuffs in the same dyebath, e.g.,

combinations of disperse and acid dyes; while in other cases, the composite material must be dyed sequentially with different types of dyestuffs and/or under different dyeing conditions. Thus it is evident that improved methods of differential dyeing of composite materials to obtain multi-shade effects are highly desirable.

Ithas now been discovered that differential dyeing of composite materials to obtain uniform tone-on-tone multi-shade' effects can be readily accomplished in a single dyebath by contacting a composite material comprising individual fibers of the same fiber-forming 2 polymeric material modified by the incorporation therein of different concentrations of the same dyereception promoter with a disperse dyestuff under dyeing conditions.

In summary, one embodiment of this invention comprises a method-for producing a differentially dyed composite material by producing a spinnable polymeric composition, producing a first fiber possessing a first concentration of a selected dye reception promoter from said composition, producing a second fiber possessing a second and different concentration of the same dye reception promoter from said composition, forming said first and second fibers into a composite material and piece dyeing said first and second fibers by contacting said composite material with a disperse dye at dyeing conditions. In another embodiment, this invention comprises producing a differentially dyed composite material by admixing a first portion of a spinnable polymeric material with a selected quantity of a selected dye reception promoter so asto produce a first concentration of dye receptionprornoter in said mixture and spinning the mixture into a first fiber, admixing another portion of the same spinnable polymeric material with a different selected quantity of the same dye reception promoter so as to produce a second i and different concentration of dye reception promoter in said mixture and spinning this mixture into a second fiber, forming said first and second fibers into a composite material and piece dyeing said first and second fibers different shades of the same color by contacting said composite material at dyeing conditions with a suitable concentration of a suitable disperse dye for a sufiicient time and at a sufficient temperature. In one still further embodiment, this invention comprises an article of manufacture which comprises a differentially piece dyed composite material of uniform polymeric composition possessing at least two different shades of the same color derived fromcontacting at least two fibers produced from the same spinnable polymeric composition, said fibers. having different concentrations of the same dye reception promoter incorporated therein, and subsequently contacting said composite material with a suitable dye.

Accordingly, an object of this invention is to produce a differentially dyed composite material.

Another object of this invention is to produce a differentially dyed composite material of polymeric composition by piece dyeing.

Another object of this invention is to produce a differentially dyed composite material of polymeric composition by piece dyeing with disperse dyes.

Another object of this invention is to produce an arti- I cle of manufacture consisting of a differentially dyed composite material. I As noted earlier, this invention comprises in summary producing a differentially dyed composite material by producing a spinnable polymeric composition and from this producing a first fiber with a first concentration of a selected dye reception promoter and producing a second fiber from the same produced composition possessing a second and difierent concentration of the same dye reception promoter. These two fibers are then formed into a composite material and the composite material is piece dyed and, as a result of the difference in concentration of the selected dye reception promoter, the first and second fibers assume different shades of the same color.

The spinnable polymeric composition used by this invention can comprise any spinnable polymeric composition -known to the art. As has been previously noted, the same polymeric composition is used to produce both fibers that subsequently are used to form the composite material. Generally, the spinnable polymeric composition can comprise a polyolefin, polyester, polyamide, or polyacrylonitrile. Stabilization systems known in the art can be added as desired. In one embodiment, polypropylene fibers made using the organometal system of titanium trichloride plus triethylaluminum chloride proved entirely satisfactory.

The fibers of this invention can be spun using any method known in the art, such as dry or, preferably, melt spinning. The term spinning also includes preparation of fibers by non-spinning methods such as fibrillation.

The dye reception promoter can be contacted with the fiber in any manner desired. In one embodiment, the dye reception promoter is admixed with a spinnable polymeric material prior to spinning. In another embodiment, the fiber is spun and the dye reception promoter applied by spraying on to the fiber as a part of or subsequent to the quenching operation. In one still further embodiment, the fiber is spun and the dye reception promoter is applied by continuously immersing the spun fiber in dye reception promoter, or solution thereof, during or following quenching.

The composite material dyed in this invention can comprise any material composed of a first and second fiber of the same polymeric composition containing different concentrations of the same dye reception promoter. Specifically, fabric goods or carpet are examples of a composite material suitable for use with this invention.

The dye reception promoters used in this invention can comprise any dye reception promoter known to alter the dye reception qualities of the particular polymeric material selected in any particular embodiment of the invention. According to this invention, different concentrations of the same dye reception-promoter are used to achieve the differentially dyed result. The invention is particularly suited for the differential dyeing of composite materials using disperse dyes.

A preferred group of dye reception promoters which have been found useful in composite materials including polyolefin, especially polymers and copolymers of monoolefins having from two to twelve carbon atoms, polyesters, polyamides and polyacrylonitriles are the complex polyamides, polyamidoesters or polyesters made according to the method of copending U.S. Pat. application Ser. No. 640,186, filed May 25, 1967 now abandoned. As a specific example, when polypropylene is selected as the polymeric fiber-forming composition, the dye-reception promoter can comprise poly [1,3- di(4-piperidyl)propane adipamide] made according to the method of said U.S. Pat. application Ser. No. 640,186.

Generally, the concentration of dye reception promoter which is incorporated into the fiber-forming polymers in accordance with the invention is in the range of zero to about 15, preferably zero to about 10, weight percent, based on the weight of the fiberforming polymer. Thus the invention contemplates composite fabrics formed from combinations of fibers containing no dye reception promoter with at least one other fiber modified with a dye reception promoter, as

well as composite fabrics formed from combinations of two or more fibers modified with a dye reception promoter in accordance with the invention. Any operable concentration of a selected dye reception promoter can be used to incorporate into either the first or the second fiber as long as the concentrations are different. In one embodiment, from about 1 to about 3 weight percent, based on the weight of the polymeric fiber, dye reception promoter was incorporated into the first fiber and from about 3 to about 8 weight percent based on the weight of the polymeric fiber was incorporated into the second fiber. In still one further embodiment, spinnable polypropylene was selected as a polymeric material and the first fiber incorporated 2 weight percent of the selected dye reception promoter and the second fiber incorporated 5 weight percent of the selected dye reception promoter. In still another embodiment, a composite fabric was formed from a polymeric fiber containing no dye reception promoter and a second fiber containing about 10 weight percent dye reception promoter. In a still further. embodiment, a composite fabric was formed from a combination of three different fibers, the first of which contained no dye reception promoter, the second of which contained 2 weight percent of dye reception promoter and the third of which contained 5 weight percent of the same dye reception promoter.

In a broad sense, preferred as dye reception promoters for the differential dyeing of synthetic fiber-forming materials with disperse dyes are those polyamides, polyarnidoesters and polyesters produced by polycondensing certain complex diamines or difunctional aminoalcohols with a dicarboxylic acid to form a polymeric composition.

The dicarboxylic acids which are suitable for use in forming the preferred dye reception promoters of the invention are those organic dicarboxylic acids which contain from 3 through 36 carbon atoms and have the formula HOOC-R-COOH wherein R is a divalent radical free from olefinic and acetylenic unsaturation. The radical can be acyclic, alicyclic, aromatic, oxygen-, sulfur-, or nitrogencontaining heterocyclic heteracyclic having no N-H, S-I-I or OH bonds, and, if not aromatic, can contain substituent aromatic groups such as phenyl or naphthyl.

Representative examples of acids that can be used to produce the dye receptive promoters are malonic, succinic, glutaric, adipic, pirnalic, suberic, azelaic, sebacic, 1 l 2-dodecanedioic, 1 1 8-octadecanedioic, dimerized oleic acid, 3,3-dimethylglutaric, 2,2,4-trimethyladipic, 1 ,4-cyclohexanedicarboxylic, 3-phenyladipic, 4-a-naphthylsuberic, l -naphthyl-2,4- cyclopentanedicarboxylic, phthalic, terephthalic, isophthalic, phenylenediacetic, 1 ,4- naphthylenedicarboxylic, 4-methylphthalic, methylimino-bis-propionic, 2,5-pyridinedicarboxylic, N-ethyl-Z,4piperidinedicarboxylic, N-propyl-2,5- pyrrolidinedicarboxylic, thiodiglycolic, 3,3-thiodipropionic, 4,4-sulfonyldibenzoic, 4,4'-sulfoxyldibenzoic, diglycolic, and 3,3'-oxodipropionic.

The complex diamines and difunctional aminoalcohols that can be used to produce the polymeric compositions which are useful as dye reception promoters -(3) arylene groups and alkyl-, cycloalkyl-,

with disperse dyes are selected from the group having the general structural formulas:

in which R is selected from the group comprising (1) straight or branched alkylene groups and cycloalkylor aryl-substituted derivatives thereof having a total of 1 through 16 carbon atoms, (2) cycloalkylene groups and alkyl-, cycloalkyl-, or aryl-substituted derivatives thereof having a total of 4 through 16 carbon atoms, or

or arylsubstituted derivatives thereof having a total of 6 through 18 carbon atoms, R being the same or different members of said R group; Y is selected from the group consisting of H, -R'NH or -R'OH, Y being the same or different radicals within said Y group; each Z is gCHor N;xisor1.

Representative examples of type I compounds are: bis( 2-pyrrolidyl )-methane, bis( 2-pyrrolidyl )propane, bis(2-piperidyl)methane, bis(4-piperidyl)-methane, 2- piperidyl(4-piperidyl )methane, l,3-di( -ethyl-2- piperidyl)propane, l,3-di( 5-methyl-2- piperidyl)propane, 2,2-di(Z-piperidyDpropane, 2,2- di(4-piperidyl)propane, 2-(2-piperidyl)-2-(4- piperidyl)propane, 1 ,3-di( 2-piperidyl)-propane, 1,3- di( 4-piperidyl )propane, 1-( Z-piperidyl -3-( 4- piperidyl)propane, 1,3-di(4-piperidyl)-2,2- dimethylpropane, 1,3-di( 2-methyl-4- piperidyl )propane, l ,3-di(4-'piperidyl)-2- cyclohexylpropane, 1 ,3-di(4-piperidyl )-2,2-dicyclohexyl-propane, l,3-di(4-cyclohexyl-2- piperidyl )propane, 1,3-di( 2,6-dicyclohexyl-4- piperidyl )propane, l ,3-di( 3-aminopropyl-4- piperidyl )propane, l,3-di( 3-amino-2-methylpropyl-4- piperidyl)propane, 1-(4-piperidyl )-3-( 3-aminopropyl- 4piperidyl)propane, l ,3-di(N-2-hydroxyethyl-4- piperidyl)propane, 1 ,3-di( N-2-hydroxypropyl-4- piperidyl )propane, l-( 4-piperidyl )-3-( N- 2hydroxyethyl-4-piperidyl )propane, l ,3-di( N-2- hydroxy-1-phenylethyl-4-piperidyl)propane, bis( 1- piperazinyl)methane, 1,3-bis[bis-1-'( 1,2-diazocyclopentane)]propane, 1-[4 3 aminopropyl)piperidyl]-l6-[4-(2- hydroxyethyl)piperazinyl]hexadecane, and the like.

Representative examples of type ll compounds are: pyrazolidine, 3-methylpyrazolidine, 3,5- dimethylpyrazolidine, imidazolidine, 2- methylimidazolidine, 4,5-dimethylimidazolidine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 2-cyclohexylpiperazine, Z-phenylpiperazine, 2,S-dicyclohexylpiperazine, 2,3-diphenylpiperazine, 2,5-diphenylpiperazine, 1,2- diazacyclohexane, 3 ,6 dicyclohexyl- 1 ,2- diazacyclohexane, 3,6-diphenyl-l ,2-diazocyclohexane, l ,3-diazocyclohexane, 2-phenyl-1 ,3-diazocyclohexane, 4,6-diphenyl- 1 ,3-diazocyclohexane, bis( N-3- aminopropyl)piperazine, bis(N-3-amino-2- methylpropyDpiperazine, l-(N-3-aminopropyl)piperazine, bis(N-2-hydroxyethyl)-piperazine, bis(N-2- hydroxypropyl)piperazine, l-(N-2-hydroxyethyl)piper- 6 azine, bis(N-Z-hydroxy-l-phenylethyl)piperazine, 1,2, 3,4,5-pentahydrocyclopentapyrimidine, 6,8- diazaspiro[4.5]decane, 1,3-diazaspiro[4.5]decane, 2,- 3-diaza-2-(2-aminoethyl)-3-(4-hydroxybutyl)- spiro[4.5]decane, and the like.

The polymeric dye reception promoters can be prepared using mixtures of two or more of the diamines and difunctional alcohols and two or more of the dicarboxylic acids described above. The operating conditions for the polycondensation reaction for the preparation of the polyamides, polyamidoesters or polyesters are well known, being described, for example, in US. Pat. No. 2,149,273 and US. Pat. No. 2,130,947. The reaction may be performed in one step or may include the formation of a salt as an intermediate step between the reaction of the initial ingredients and the production of the desired polyamides, polyamidoesters or polyesters therefor as described in. US. Pat. No. 2, 130,- 947. For example, when a one-step reaction is used the polyamide, polyamidoester or polyester can be prepared by heating approximately equimolar amounts of diamine or difunctional alcohol and the dicarboxylic acid at a temperature in the range of 210 to 575 F, preferably 300 to 540 F, in the presence or absence of suitable solvents or diluents with or without suitable condensing agents, at superatmospheric, atmospheric or subatmospheric pressure for periods of 0.1 to 50 hours. The reaction is preferably carried out in the absence of air and sometimes the addition of antioxidants is desirable. A small excess of either the amine or difunctional alcohol or the dicarboxylic acid may be used to extend the control of the reaction. The product of reaction has an inherent viscosity in methyl alcohol or meta-cresol at 30 C in the range of 0.05 to 1.0 dl/g.

The composite material can be piece dyed according to this invention in any manner that results in the dyeing of the entire composite material or a large portion thereof at substantially the same time. As examples, the entire composite material can be immersed in a bath of the dye, or the dye can be padded on, or can be sprayed on, or the like. Additionally large portions, such as rolls of the fabric or carpet, can be dyed continuously by immersion in a bath prior to being placed on rolls.

The dye useful in this invention can comprise any dye known to dye the particular polymeric composition selected and contacted with a suitable dye reception promoter. The invention is particularly suited for use with disperse dyes. Examples of dyes that are commercially available in use for this invention are disperse dyes such as (3.1. 62500, (1.1. 11855, Foron Blue ER (Sandoz Chemical Works), Cl. Disperse Yellow 50, Cl. Disperse Yellow 54, Cl. Disperse Red 55, Cl. Disperse Blue 116, Cl. 26070, Genacron Blue GR (General Aniline & Film), (ll. Disperse Blue 73, and lPolydye Red BC (Inmont Corp). Wetting agents and pH adjusters can also be added to the selected dye to produce optimum dyeing characteristics. In a specific embodiment, polypropylene was selected as a spinnable material, poly[1,3-di( 4-piperidyl)propane adipamide] as a dye receptor, and Terasil Blue GL (CI. Disperse Blue 73) ite material. The range of concentrations can vary from about 0.1 to about 2.0 weight percent on weight of fiber, or even higher or lower. According to this invention, the time used for piece dyeing can comprise any time that will result in differentially dyeing the composite material. Generally, the range from about to about 300 minutes is satisfactory, although higher and lower ranges are possible. The temperature of the dyeing medium during the dyeing process can comprise any temperature that will result in differentially dyeing the composite material. Generally, the temperatures can range from about 50 C to about 150 C, although higher or lower ranges are within the scope of this invention.

Various modifications of this invention can be made in view of the foregoing disclosure and appended claims without departing from the spirit or scope thereof.

EXAMPLE I Polypropylene was polymerized with a diethylaluminum chloride/TiCl --1/3 AlCl catalyst to give a polymer having a melt flow of 12 dg/min (ASTM D 1238-62T, Condition L). The following materials well known in the art were added to the polymer for stabilization and delustering: 0.05 php (parts by weight per 100 parts by weight polymer) 2,6-di-tert-butyl-4- methylphenol, 0.15 php di-n-octadecyl-3,S-di-tertbutyl-4-hydroxybenzyl phosphonate, 0.3 php distearylthiodipropionate, 0.5 php 2-(2-hydroxy-3,5- di-tert-butylphenyl)-5-chloro-2, 1 ,3-benzotriazole, O. 1 php dioctylphosphite, and 0.4 php titanium dioxide. A first portion of this material was admixed with 2 weight percent poly[1',3-di-(4-piperidyl)propane adipamide] based on the weight of the spinnable polypropylene. A second portion of this same spinnable polypropylene was admixed with 5 weight percent of the same dye reception promoter based on the weight of the spinnable polypropylene. A first yarn was produced from the fibers of the first portion and a second yarn produced from the fibers of the second portion by melt spinning at 525 F. The physical properties of the first and second yarns are given in the following table:

utes at C. All percentages and ratios are on weight of fabric.

The resulting carpet was examined and it was noted that the yarn from which the fibers from the first composition were produced had achieved a light blue intensity of uniform and marketable quality, while the yarn formed from the fibers of the second composition had achieved a very deep uniform blue of entirely marketable quality. Thus applicant has demonstrated the differential dyeing of a composite material of the same polymeric composition by producing fibers from the same polymeric composition containing different concentrations of a selected dye reception promoter and has in this example produced a differentially dyed polypropylene carpet of marketable quality. The example further demonstrates that composite materials can, in accordance with this invention, be successfully differentially dyed to a multi-shade effect using only disperse dyes as the dyeing medium.

EXAMPLE ll To a polypropylene having a melt flow of 12 dg/min there was added 0.05 php 2,6-di-tert-butyl-4- methylphenol, 0.15 php di-n-octadecyl-3,5-di-tertbutyl-4-hydroxybenzyl phosphonate, 0.3 php distearylthiodipropionate, 0.5 php 2-(2-hydroxy-3,5- di-tert-butylphenyl)-5-chloro-2,1,3-benzotriazole, 0. 1 php dioctylphosphite and 0.4 php titanium dioxide. As used in this example and elsewhere in the specification, php is defined as parts by weight per 100 parts by weight polymer. The resulting mixture was divided into three portions. To a first portion there was added 2 weight percent, based on the weight of the polypropylene, of poly[1,3-di(4-piperidyl)propane adipamide] dye reception promoter. To a second portion there was added 5 weight percent, based on the weight of the polypropylene, of the same dye reception promoter. The third portion contained no dye reception promoter. Yarns were produced from the fibers of each of the three individual portions by melt spinning at 525 F. Yam properties were:

""ASTM D 2256-64T ""Yellowness index is determined on 21 Signature Model LSD-1 Color Eye manufactured by Instrument Development Laboratories. slhwe are? 99 2:2 13.--

Both yarns were then applied to carpet backing so as to produce a composite carpet. The carpet was then piece dyed by immersion in an aqueous solution containing, as the sole dyestuff, 0.5 weight percent Terasil Blue BGL (C.l. Disperse Blue 73), 2 weight percent wetting agent, and suflicient formic acid to result in a pH of 5 at a 50:1 liquor ratio. The Terasil Blue BGL is a disperse dye (C.I. Disperse Blue 73) and was the sole dyestuff employed. The carpet was entered at 50 C, raised to the boiling point, held for 1 hour, rinsed and secured in aqueous 2 percent wetting agent for 15 min- Three readings are taken: X.Y. and Z and the ASTM D 2256-64T Yellowncss index is as determined in Example I.

to produce a composite carpet. The carpet was piece dyed by immersion in an aqueous solution containing 0.5 percent Terasil Blue BGL (Color Index Disperse Blue 73), 2 percent wetting agent, and sufficient formic acid to result in a pH of 5 at a 50:1 liquor ratio. The carpet was entered at 50 C, raised to the boiling point, held one hour, rinsed and scoured in aqueous 2 percent wetting agent for minutes at 50 C. All percentages and ratios are on weight of fabric.

The resulting carpet was examined and it was noted that the fibers containing 2 weight percent dye reception promoter had achieved a light blue intensity of uniform and marketable quality, the fibers containing 5 weight percent dye reception promoter had achieved a deep blue intensity of uniform and marketable quality, while the fiber containing no dye reception promoter retained its original white color. The overallcoloration showed a great contrast between the two blue tones and the white shade. This example demonstrates the differential dyeing of a composite material in a single dyebath using a single disperse dyestuff in accordance with the invention.

EXAMPLE III moter in amounts ranging from 0 to 15 weight percent, based upon weight of polymer;

wherein said first and second fibers are formed from the same polyolefin;

wherein said promoter in each of said spinnable polymeric compositions isthe same;

wherein the amount of said promoter in said first fiber is different from the amount of said promoter in said second fiber; and

wherein said dyereception promoter is selected from the group consisting of the polymeric reaction products formed from the polycondensation of a dicarboxylic acid having the formula HOOC- R-COOI-l, wherein R is a divalent radical free from olefmic and acetylenic unsaturation and having from 3 to 36 carbon atoms, and a compound selected from the group consisting of compounds having the formulas in wherein each R is individually selected from the group adipamide] based on theweight of the spinnable polyamide. A second portion of the same spinnable polyamide is admixed with 1 weight percent of poly[ l,3-di(4- piperidyl)propane adipamide], based on the weight of the spinnable polyamide. A first yarn is produced from the fibers of the first portion and a second yarn is pro-. duced from the fiber of the second portion by melt spinning at 560 F. Knits of these yarns are dyed with.

disperse dyes using conventional dyeing procedure. Vi-

sualinspection of the dyed composite material demonstrates that composite fabrics woven from polyamide yarns can be differentially dyed to obtain tone-on-tone colorations when the polyamides are modified in accordance with this invention.

EXAMPLE IV Yarns were formed from a.fiber-forming polyamide [nylon 66, poly(hexamethylene adipamide)] containing -10 php poly[1,3-di(4-piperidyl)P T0pane adipamide] dye receptionpromoter and no dye reception promoter, respectively, by melt spinning at 560 F.-

Knits of these two yarns were dyed with disperse dyes using'conventional dyeing procedure. Visual inspection of the dyed composite material demonstrate that composite fabrics woven from polyamide yarns can be successfully dyed with disperse dyestuffs when the polyamides are modifed in accordance with the invention.

Reasonable variations and modifications are possible within the scope of the foregoing disclosure and the ap-. pended claims to the invention.

, I claim:

1. A method for differential dyeing of composite materials comprising the steps of:

a. forming a first fiber from a spinnable polymeric composition comprising a fiber-forming polyolefin having incorporated therein a dye reception promoter in amounts ranging from 0 to 15 weight per- 7 cent, based upon weight of polymer;

b. forming a second fiber from a spinnable polymeric having incorporated therein a dye reception proconsisting of alkylene, cycloalkylalkylene, arylalkylene, cycloalkylene, alkylcycloalkylene, cycloalkylcycloalkylene, arylcycloalkylene, arylene, alkylarylene, cycloalkylarylene and arylarylene radicals having from 1 to 18 carbon atoms; Y is individually selected from the group consisting of -l-l-RNH and -R'Ol-l, R being as previously defined; Z is CH or 2-; N; and x is 0 or l; r I

c. forming said first and second ite material; and

d. contacting said composite material with a disperse dye at dyeing conditions. A

2. The method of claim 1 wherein the amount of said dye reception promoter in said first fiber is in the approximate range of 1 to 3 weight percent and the fibers into a composamount of dye reception promoter in said'second fiber A is in the approximate range of 3 to 8 weight percent.

3. The method of claim 2 whereinsaid dye reception promoter is .poly(.1,3-di(4-piperidyl)propane adipamide). v t i 4. The method of claim 3 wherein saidpolyolefin is polypropylene.

5. A method for differential dyeing of a composite material comprising the steps of:

a. forming a first fiber from a spinnable polymeric composition comprising a'fiber-forrning polyamide having incorporated therein a dye reception promoter in amounts ranging from 0 to 15 weight percent, based upon weight of polymer; b. forming a second fiber from a spinnable polymeric composition comprising a fiber-forming polyamide having incorporated therein a dye reception promoter in amounts ranging from 0 to 15 weight percent, based upon weight of polymer; wherein said first and second fibers are formed from the same polyamide; wherein said promoter in each of said spinnable polymeric compositions is the same; wherein the amount of said promoter in said first fiber is different from the amount of promoter in Said second fiber; and

wherein each R is individually selected from the group consisting of alkylene, cycloalkylalkylene, arylalkylene, cycloalkylene, alkylcycloalkylene, cycloalkylcycloalkylene, arylcycloalkylene, arylene, alkylarylene, cycloalkylarylene and arylarylene radicals having from 1 to 18 carbon atoms; Y is individually selected from the group consisting of -H-RNH and -R'OH, R being as previously defined; Z is E CH or E N; and x is O or 1;

c. forming said first and second fibers into a composite material; and

d. contacting said composite material with a disperse dye at dyeing conditions.

6. The method of claim 5 wherein the amount of dye reception promoter in said first fiber is in the approximate range of l to 3 weight percent and the amount of dye reception promoter in said second fiber is in the approximate range of 3 to 8 weight percent.

7. The method of claim 6 wherein said dye reception promoter is poly( l,3-di(4-piperidyl)propane adipamide).

8. The method of claim 7 wherein said fiber-forming is poly(hexamethylene adipamide).

9. An article of manufacture comprising a differentially dyed composite material of uniform polymeric composition possessing at least two different shades of the same color derived from producing at least two fibers produced from the same spinnable polyolefin, said fibers having incorporated therein different concentrations of the same dye reception promoter, wherein said promoter is selected from the group consisting of the polymeric reaction products formed from the polycondensation of a dicarboxylic acid having the formula HOOC-R-COOH, wherein R is a divalent radical free from olefinic and acetylenic unsaturation and having from 3 to 36 carbon atoms, and a compound selected from the group consisting of compounds having the forwherein each R is individually selected from the group consisting of alkylene, cycloalkylalkylene, arylalkylene, cycloalkylene, alkylcycloalkylene, cycloalkylcycloalkylene, arylcycloalkylene, arylene, alkylarylene, cycloalkylarylene and arylarylene radicals having from 1 to 18 carbon atoms; Y is individually selectedfrom the group consisting of -H-R'NH and -ROH,R being as previously defined; Z is E H or E N; and x is Q or 1, said composite material having been dyed with a disperse dye.

10. An article of manufacture according to claim 9 wherein said dye reception promoter is poly( l,3-di(4- piperidyl)propane adipamide).

11. An article of manufacture according to claim 10 wherein said fiber-forming polyamide is poly(hexamethylene adipamide).

12. An article of manufacture according to claim 9 wherein said article is a carpet.

13. An article of manufacture according to claim 9 wherein said dye reception promoter comprises poly( 1- ,3-di(4-piperidyl)propane adipamide).

14. An article of manufacture according to claim 13 wherein said polyolefin comprises polypropylene.

15. An article of manufacture according to claim 9 wherein said article comprises a carpet.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,820,949 Robert F. Johnson Date June 28, 1974 It is certified that error appears in the above-identified patent and that said letters Patent are hereby corrected as shown below:

Claim 8, column 11, line 40, after "fiber-forming" insert polyamidle---.

Claim 9, column 12, line 20, "or should be deleted- Claim 10, column 12, line 31, "claim 9" should read claim 16 Claim 12, column 12, line 37, "claim 9" shouhd read claim 16 In column 12, after claim 15, insert the following claim:

16. An article of manufacture comprising a differentially dyed composite material of uniform polymeric composition possessing at least two different shades of the same color derived from producing at least two fibers produced from the same spinnable polyamide, said fibers having incorporated therein different concentrations of the same dye reception promoter, wherein said promoter is selected from the group consisting of the polymeric reaction products formed from the polycondensation of a dicarboxylic acid having the formula HOOC-R-COOH, wherein R is a divalent radical free from olefinic and acetylenic unsaturation and having from 3 to 36 carbon atoms, and a compound selected from the group consisting of compounds having the formulas N x\ Z R' Z N Y, or

wherein each R is individually selected from the group consisting of alkylene, cycloalkylalkylene, arylalkylene, cycloalkylene, alkylcycloalkylene, cycloalkylcycloalkylene, arylcycloalkylene, arylene, alkylarylene, cycloalkylarylene and arylarylene radicals having from 1 to 18 carbon atoms; Y is individually selected from the group consisting of HR'NH and R'OH, R' being as pre-- viously defined; Z is ECH or 5N; and x is O or 1, said composite material having been dyed with a disperse dye.

Signed and sealed this 19th day of November 197A.

(SEAL) Attest:

MCCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents 

2. The method of claim 1 wherein the amount of said dye reception promoter in said first fiber is in the approximate range of 1 to 3 weight percent and the amount of dye reception promoter in said second fiber is in the approximate range of 3 to 8 weight percent.
 3. The method of claim 2 wherein said dye reception promoter is poly(1,3-di(4-piperidyl)propane adipamide).
 4. The method of claim 3 wherein said polyolefin is polypropylene.
 5. A method for differential dyeing of a composite material comprising the steps of: a. forming a first fiber from a spinnable polymeric composition comprising a fiber-forming polyamide having incorporated therein a dye reception promoter in amounts ranging from 0 to 15 weight percent, based upon weight of polymer; b. forming a second fiber from a spinnable polymeric composition comprising a fiber-forming polyamide having incorporated therein a dye reception promoter in amounts ranging from 0 to 15 weight percent, based upon weight of polymer; wherein said first and second fibers are formed from the same polyamide; wherein said promoter in each of said spinnable polymeric compositions is the same; wherein the amount of said promoter in said first fiber is different from the amount of promoter in said second fiber; and wherein said dye reception promoter is selected from the group consisting of the polymeric reaction products formed from the polycondensation of a dicarboxylic acid having the formula HOOC-R-COOH, wherein R is a divalent radical free from olefinic and acetylenic unsaturation and having from 3 to 36 carbon atoms, and a compound selected from the group consisting of compounds having the formulas
 6. The method of claim 5 wherein the amount of dye reception promoter in said first fiber is in the approximate range of 1 to 3 weight percent and the amount of dye reception promoter in said second fiber is in the approximate range of 3 to 8 weight percent.
 7. The method of claim 6 wherein said dye reception promoter is poly(1,3-di(4-piperidyl)propane adipamide).
 8. The method of claim 7 wherein said fiber-forming is poly(hexamethylene adipamide).
 9. An article of manufacture comprising a differentially dyed composite material of uniform polymeric composition possessing at least two different shades of the same color derived from producing at least two fibers produced from the same spinnable polyolefin, said fibers having incorporated therein different concentrations of the same dye reception promoter, wherein said promoter is selected from the group consisting of the polymeric reaction products formed from the polycondensation of a dicarboxylic acid having the formula HOOC-R-COOH, wherein R is a divalent radical free from olefinic and acetylenic unsaturation and having from 3 to 36 carbon atoms, and a compound selected from the group consisting of compounds having the formulas
 10. An article of manufacture according to claim 9 wherein said dye reception promoter is poly(1,3-di(4-piperidyl)propane adipamide).
 11. An article of manufacture according to claim 10 wherein said fiber-forming polyamide is poly(hexamethylene adipamide).
 12. An article of manufacture according to claim 9 wherein said article is a carpet.
 13. An article of manufacture according to claim 9 wherein said dye reception promoter comprises poly(1,3-di(4-piperidyl)propane adipamide).
 14. An article of manufacture according to claim 13 wherein said polyolefin comprises polypropylene.
 15. An article of manufacture according to claim 9 wherein said article comprises a carpet. 